CN109860676A - A kind of film electrode structure, fuel cell and battery pile - Google Patents

A kind of film electrode structure, fuel cell and battery pile Download PDF

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Publication number
CN109860676A
CN109860676A CN201910280009.5A CN201910280009A CN109860676A CN 109860676 A CN109860676 A CN 109860676A CN 201910280009 A CN201910280009 A CN 201910280009A CN 109860676 A CN109860676 A CN 109860676A
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electrode
layer
separating materials
oxide
cathode
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区定容
李致朋
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Shenzhen Zhiyuan Power Technology Co Ltd
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Shenzhen Zhiyuan Power Technology Co Ltd
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Abstract

A kind of film electrode structure, fuel cell and battery pile, belong to field of batteries.Film electrode structure is applied to battery, especially fuel cell.Film electrode structure has multilayered structure and first electrode layer, the second electrode lay and electrolyte layer including successively lamination contact arrangement, and electrolyte layer is between first electrode layer and the second electrode lay.One of first electrode layer and the second electrode lay and the two have network-like structure.Wherein, network-like structure includes separating materials layer and optional electrode material layer.The thermal expansion coefficient of separating materials layer is less than or equal to the thermal expansion coefficient of electrolyte layer.Degree of being mutually matched is high between electrode and electrolyte in film electrode structure, is not easy to remove, be detached from each other because the difference of thermal expansion is too big each other.

Description

A kind of film electrode structure, fuel cell and battery pile
Technical field
The present invention relates to field of batteries, in particular to a kind of film electrode structure, fuel cell and battery pile.
Background technique
With the fast development of mobile Internet and Internet of Things, various portable mobile apparatus (such as palm PC, mobile phone, The various e-machines such as various wearable devices such as wrist-watch) it is more more and more universal.In use, equipment some in this way can usually be related to To continuation of the journey problem, i.e. electricity shortage.And with the prosperity of semiconductor technology, various equipment are constantly to miniaturization.To have Power supply of the fuel cell of special performance for these equipment has quite ideal prospect.
Fuel cell is exactly the device for the chemical energy of chemical reaction being converted into electric energy.It is made with fuel and oxidant For the raw material that generates electricity.There are many type of fuel cell, classification method also there are many.
As an important types of fuel cells, solid oxide fuel cell (Solid Oxide Fuel Cell, SOFC) Has the advantages that itself uniqueness.And also there is more excellent service performance and value accordingly.For example, solid oxide fuel is electric Pond has relatively high operating temperature (such as 800~1000 DEG C).Solid oxide fuel cell as a kind of all solid state device, Two-phase (gas-solid) reaction is related merely to during its fuel reaction, thus, without carrying out complicated electrolyte management, Ke Yi Simplify structure to a certain extent.
There is membrane structure design in current some SOFC.This structure based on SOFC, manufacturing process need special It does not investigate, in conjunction with conditions such as its operating temperatures, using there is also certain problems.These all limit template SOFC's Further development.
Normally, the main problem of SOFC first is that: during actual make and use, template SOFC is often showed The situations such as crackle easy to form, cracking, removing out.
The information disclosed in the background technology section is intended only to deepen understanding of the general background technology to the present invention, and It is not construed as recognizing or implying in any form that the information constitutes the prior art known to those skilled in the art.
Summary of the invention
For improve, even solve the problems, such as it is in the prior art at least one, the invention proposes a kind of film electrode structures, combustion Expect battery and battery pile.
The present invention is implemented as follows:
In a first aspect, example of the invention provides a kind of film electrode structure.
Film electrode structure in example can be applied to battery, especially fuel cell, especially solid oxide fuel Battery.
Film electrode structure has multilayered structure.
Film electrode structure includes first electrode layer, the second electrode lay and the electrolyte layer of successively lamination contact arrangement, and And electrolyte layer is between first electrode layer and the second electrode lay.
One of first electrode layer and the second electrode lay and the two have network-like structure.
Wherein, network-like structure includes separating materials layer and optional electrode material layer, and optional electrode material layer Between electrolyte layer and electrode material layer.
The thermal expansion coefficient of separating materials layer is less than or equal between the thermal expansion coefficient of electrolyte layer.
Network-like structure is divided electrode, it is made to be subdivided into multiple relatively smaller areas by complete continuous structure Domain continuously or discontinuously structure, to play the effect of release stress.By being split to the electrode in film electrode structure, The thermal expansion of electrode is set to be inhibited and be weakened to a certain extent, so as to preferably avoid the heat between electrode and electrolyte swollen Swollen mismatch.Since the thermal expansion mismatch between electrode and electrolyte is reduced, film electrode structure stress as caused by mismatch also by Greatly reduce, excessively adds up caused the problems such as cracking, removing by stress so as to avoid between electrode and electrolyte.
With reference to first aspect, in some optional examples of the first possible embodiment of the invention, separating materials Layer is Continuum Structure or discrete bodies structure.
Optionally, the shape of Continuum Structure includes the first regular figure or the first irregular figure.
Optionally, the first regular figure includes array shape, honeycombed, and the hole of array shape is triangle, quadrangle or polygon Shape.
Optionally, separating materials layer is discrete bodies structure, and the shape of discrete bodies structure includes Second Rule figure or second Irregular figure.
Optionally, Second Rule figure is forked.
Various structures appropriate are arranged by selection in separating materials layer according to different requirements, can reach electrode point Being segmented into multiple smaller regions is advisable.Different separating materials layer structures can be as required according to the difficulty or ease progress for realizing technique Selection.Since separating materials layer has the implementation of plurality of optional, the flexibility of film electrode structure production can be improved.
With reference to first aspect or the first possible embodiment of first aspect, at second of first aspect present invention In some optional examples of possible embodiment, separating materials layer has the direction by first electrode layer to the second electrode lay Thickness, and with a thickness of 1~50 micron.
Optionally, with a thickness of 6~45 microns.
Optionally, with a thickness of 16~30 microns.
Optionally, with a thickness of 20~26 microns.
The size of film electrode structure is usually one of an important factor for limiting its application scenarios and field.Therefore, based on suitable Work as demand, comprehensive consideration its production, technique, raw material and in terms of the case where, it will be beneficial for adjusting thickness appropriate 's.As a kind of pair of advantageous selection of portable battery, it will be appropriate for controlling the thickness of separating materials layer.Normally, divide Material layer is made the too thick easy combination influenced between electrode and electrolyte.Of course, separating materials layer is made too Bao Ze may cause the obvious rising of the difficulty of manufacture craft, and may thus cause under its segmentation effect to electrode Drop.
With reference to first aspect, in some optional examples of the third possible embodiment of the first aspect of the present invention In, the material of separating materials layer includes doped or non-doped cerium oxide, doped or non-doped zirconium oxide, aluminium oxide, magnalium The combination of any one or more in spinelle, silicate.
Optionally, the cerium oxide of doping and the zirconium oxide of doping are all made of rare earth element and are doped, and rare earth element packet It includes one or more.
It is an optional alternative condition that separating materials layer, which has ion appropriate (including oxonium ion) electric conductivity,.In addition, It is apparent that wishing the stability that separating materials layer has been kept in the whole life cycle of film electrode structure.Select above-mentioned point The requirement of ionic conductivity and stability can be met to a great extent by cutting material layer material.
With reference to first aspect or the third possible embodiment of the invention, at the 4th kind of the first aspect of the present invention In some optional examples of possible embodiment, first electrode layer and the second electrode lay all have network-like structure, and The material of separating materials layer in the material and the second electrode lay of separating materials layer in one electrode layer is identical or different.
It is apparent that being carried out to improve the performance and stability of film electrode structure to first electrode layer and the second electrode lay Segmentation can effectively make the thermal expansion mismatch problems of the two be improved in a manner of relative ideal, even solve.
In different batteries, the separating materials layer in first electrode and second electrode, which can according to need, to be selected by each Kind suitable material production.In view of the possibility of replacement or alternative materials is difficult in manufacture craft, perhaps can using identical material Bring technologic convenience.It certainly, can also be in the condition for being suitably modified technique according to the demand of different function and performance Under, select different materials.
With reference to first aspect, in some optional examples of the 5th kind of possible embodiment of the first aspect of the present invention In, first electrode layer is anode, and anode is metal electrode or cermet electrodes.
Optionally, the material of anode is nickel or nickel alloy or nickeliferous ceramics.
As a kind of application in a fuel cell, anode be can choose as micropore gas diffusion electrode.Correspondingly, anode The selection of material can be metal simple-substance electrode or ceramal or cermet (such as metal oxide) electrode.
Such electrode can satisfy the needs of stability, fuel mass transfer etc., be conducive to electrode reaction it is normal into Row.
With reference to first aspect, in some optional examples of the 6th kind of possible embodiment of the first aspect of the present invention In, the second electrode lay is cathode, and cathode is metal oxide electrode.
Optionally, the material of metal oxide electrode is ternary alloy three-partalloy oxide or quaternary alloy oxide.
Optionally, the first element combinations of metallic element in ternary alloy three-partalloy oxide or second element combination, wherein first Element combinations include lanthanum, strontium, cobalt, and second element combination includes samarium, strontium, cobalt, and the metallic element in quaternary alloy oxide includes Lanthanum, strontium, cobalt, iron.
As a kind of application in a fuel cell, similarly with anode, cathode be can choose as micro-porous electrode.It is such Electrode can satisfy compound etc. the needs of electronics conduction, ion, be conducive to being normally carried out for electrode reaction.
Correspondingly, the selection of cathode material can be such as above-mentioned material, or such as ceramic material (ceramal), either The perovskite or strontium doping lanthanum manganite of such as semiconductor structure.
With reference to first aspect, in some optional examples of the 7th kind of possible embodiment of the first aspect of the present invention In, the material of electrolyte layer includes undoped or doping metal oxide.
Optionally, metal oxide includes zirconium oxide and cerium oxide.
Optionally, the doped chemical in the metal oxide of doping is rare earth element, and rare earth element includes a kind of or more Kind.
The selection of electrolyte can usually be investigated: oxygen ionic conductivity is high;Electronic conductivity is low and impermeable reaction gas Body.By selection such as rear-earth-doped electrolyte, electrolyte can be made still to have at temperature appropriate such as middle cryogenic conditions Cation conductivity.
In second aspect, example of the invention provides a kind of fuel cell.
Fuel cell includes above-mentioned film electrode structure.
The above film electrode structure can be produced and use in the form of a film, fire so as to be used for soild oxide such as Expect battery.Its structure is more compact, reduces numerous severe electrolyte management requirement, or even in some schemes adjusted, also It is able to bear the problem of overload, low load or short circuit.It further, can also be in energy conservation based on this solid oxide fuel cell Etc. obtain original performance.In addition, it can also be modulated to use under conditions of relatively-high temperature, thus, using neck Domain is wider.
In the third aspect, example of the invention provides a kind of battery pile.
Battery pile includes at least two fuel cells as the aforementioned, and is passed through between two adjacent fuel cells Bipolar plates connection.
The application in the form of battery pile by fuel cell, higher voltage and power output can be obtained, to meet The power demand of actual various equipment.
The utility model has the advantages that
In film electrode structure provided in an embodiment of the present invention, electrode (first electrode layer and/or the second electrode lay) is passed through Separating materials layer is separated, and electrode is made to be provided with subtleer structure.The thermal expansion of electrode due to separating materials layer and Suitably inhibited, so that the conduction for the stress for generating thermal expansion and local accumulation are also limited, therefore, electrode and electrolyte Between removing, cracking be also able to preferably be prevented, so as to a certain degree improve based on the electricity for changing film electrode structure The service life in pond (such as fuel cell) and performance.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the structural schematic diagram at the first visual angle of the first film electrode structure in example of the present invention;
Fig. 2 shows the structural schematic diagrams at the second visual angle of film electrode structure shown in FIG. 1;
Fig. 3 is shown as the structural schematic diagram at the second visual angle of second of film electrode structure in example of the present invention;
Fig. 4 is shown as the structural schematic diagram at the second visual angle of the third film electrode structure in example of the present invention;
Fig. 5 is shown as the structural schematic diagram at the second visual angle of the 4th kind of film electrode structure in example of the present invention;
Fig. 6 is shown as the structural schematic diagram at the first visual angle of the 5th kind of film electrode structure in example of the present invention.
Icon: 100- film electrode structure;102- anode;103- electrolyte layer;104- cathode;105- separating materials layer; The region 1041a-;105a- separating materials layer;The region 1041b-;105b- separating materials layer;The region 1041c-;105c- divides material The bed of material;The region 1041d-;105d- separating materials layer;200- fuel cell;204- cathode;205- separating materials layer.
Specific embodiment
In realizing process of the present invention, inventor has found under study for action, although solid oxide fuel cell has it solely Special advantage, but there is also certain urgent problems to be solved.
For example, the problems such as battery is easy to appear cracking, structure sheaf peels off.Such problems either in its manufacturing process, Still there is performance in use.For such a problem, the prior art has carefully been investigated, in correlative study and technology Generally, it is considered that this is because caused by combination between exfoliation layer is insecure.Inventor has found to cause in further studying One main cause of the problem is the mismatch problems between different structure layer.For example, due to heated between different structure layer (principal element), the degree difference by cold events are expanded, when opposite deformation (expansion) occurs, the two cannot match well It closes.It can lead to the accumulative of stress between the big substance of thermal expansion coefficient and the small substance of thermal expansion coefficient by differences in expansion, in turn Cause the situation of faying face being separated from each other.
For example, cathode problem: the perovskites cathode such as LSC, LSCF, SSC exists in some solid oxide fuel cell Catalytic activity and conductivity with higher under middle low temperature, but thermal expansion coefficient is significantly higher than electrolyte.Alternatively, its anode is asked Topic: as Ni content increases, the thermal expansion coefficient of Ni metal anode increases.In order to keep good thermal expansion matching, often adopt With lower Ni content, the decline of anode conducting performance.
For this, inventor thinks to improve or alleviate above ask by the thermal expansion coefficient adjustment to different structure layer Topic.
Although person can be adjusted by the selection to material, it is contemplated that the own characteristic of battery, as electrode is anti- It answers, working environment etc., only changing material may result in some degradations of battery itself.In other words, only with adjustment The material of electrode and/or electrolyte realizes the problem of matching of thermal expansion perhaps can cause other, and leads to such trial It is possible and undesirable or not be better choice.
In view of this, in the present example, inventor attempts to improve the film electrode structure of battery.
In example, by being split to electrode, the electrode formation multiple regions more tiny relative to full size, and Separating materials layer is constructed at the boundary of the adjacent area of multiple regions, and using the separating materials layer as two neighboring region Boundary.
Due to the presence of the separating materials layer as boundary, the structural intergrity of electrode as a whole is broken, Deformation (volume expansion) as a whole will disperse in each region and become smaller deformation.The thermal expansion shape of such electrode Varying stress is released, and is not easy to separate with electrolyte.Simultaneously as the thermal expansion coefficient of separating materials layer is by choosing appropriate It selects, is also less likely to occur biggish volume change, thus be also easier to be adapted to electrolyte and electrode.
Below with reference to attached drawing, film electrode structure, fuel cell and the battery pile in example of the present invention are carried out more detailed Most explanation.
In order to which the technical solution of the embodiment of the present invention is more clearly understood, the embodiment of the present invention is with soild oxide It is illustrated for film electrode structure in fuel cell.
Fuel cell generally includes anode, cathode, electrolyte and some other support system or device, for example, carrying out Shell, fuel supply device, collector of encapsulation etc..
It should be understood that since fuel cell is the equipment that the chemical energy of fuel is converted into electric energy, and in order to It realizes and concentrates or power to large number of equipment, fuel cell is usually used in a manner of battery pile.I.e. by multiple fuel cell units Conjunction is carried out using to provide more appropriate voltage and power.
And for the fuel cell system of such battery pile, the fuel cell in practical application can also correspond to outfit fuel (such as hydrogen, hydrogen-rich reformed gas, hydrazine/diamine) feeding mechanism.Or it can also be equipped with some gases, liquids recovery as needed System etc..
Film electrode structure in example of the present invention has multilayered structure.That is film electrode structure be a certain number of structure sheafs with The mode of stacking is arranged, and can be combined together by way of sintering between each layer.
In example, film electrode structure includes first electrode layer, the second electrode lay and the electrolysis of successively lamination contact arrangement Matter layer, and electrolyte layer is between first electrode layer and the second electrode lay.Such film electrode structure can be applied to In tubular type or board-like SOFC.
In order to inhibit and weaken the stripping problem between electrode and electrolyte, in example, first electrode layer and second electrode One of layer and the two have network-like structure.I.e. first electrode layer has network with network-like structure or the second electrode lay Shape structure or first electrode layer and the second electrode lay all have network-like structure.Corresponding to SOFC, anode has network-like structure Or there is cathode network-like structure or anode and cathode to all have network-like structure.
Just it has been observed that electrode district is divided into multiple regions by network-like structure.In as an example, network-like structure includes Separating materials layer and optional electrode material layer.Wherein, optional electrode material layer be located at electrolyte layer and electrode material layer it Between.
In other words, network-like structure can be is made of separating materials layer completely.In such an example, separating materials layer Capable of extending outwardly from electrolyte layer, (extending direction can be electrolyte layer to the second electrode lay and/or electrolyte layer to One electrode layer), and run through corresponding electrode.As separating materials layer from electrolyte to first electrode layer extend, and through first electricity Pole layer.In optional scheme, the extension of separating materials layer be carried out in a manner of perpendicular to electrolyte, alternatively, can be with Surface with electrolyte layers is at non-perpendicular fashion (such as acute angle, including 30 °, 45 °, 55 °, 60 ° or obtuse angle, including 120 °, 130 °).
Alternatively, network-like structure can also be by separating materials layer and electrode material layer (first electrode layer or the second electrode lay) It collectively forms, and separating materials layer is between electrolyte layer and electrode material layer.For example, having in first electrode layer network-like In the example of structure, the surface of electrolyte layer forms separating materials layer and first electrode layer, and first electrode layer is to cover net Network shape structure (i.e. the separating materials layer of network-like structure).That is, network-like structure can also be by separating materials layer and electrode Material layer collectively forms, and separating materials layer, in the scheme between electrolyte layer and electrode material layer, separating materials layer is simultaneously Non- penetrating electrode.
Simultaneously in order to avoid the selection of the separating materials layer for the composition network-like structure being introduced into as segmentation electrode is lost When and the problem of cause mismatch again, the thermal expansion coefficient of separating materials layer is selected.For example, the thermal expansion coefficient of separating materials layer Less than or equal to the thermal expansion coefficient of electrolyte layer.Thermal expansion coefficient in view of electrode in general SOFC is to be greater than electrolysis significantly The thermal expansion coefficient of plasma membrane, therefore, the thermal expansion coefficient of separating materials layer can choose smaller in example, i.e., than electrode material Thermal expansion coefficient is much smaller.
Material selection for film electrode structure, those skilled in the art can according to need the various materials appropriate of selection Expect, it is not particularly limited in invention.Some example effects, can make for the different structure layer in film electrode structure Following example shape is enumerated out.
For constituting one of the component of network-like structure, the material selection of separating materials layer is as follows: for example, separating materials layer Material include doping cerium oxide, undoped cerium oxide, the zirconium oxide of doping, undoped zirconium oxide, aluminium oxide, magnalium The combination of any one or more in spinelle, silicate.Wherein, a variety of combinations can be the combination of the two (as aoxidized Aluminium and magnesium aluminate spinel;Magnesium aluminate spinel and silicate;Cerium oxide and the zirconium oxide of doping of doping etc.) or three Combination is (such as the zirconium oxide and aluminium oxide of the cerium oxide, doping that adulterate;Zirconium oxide, aluminium oxide and the magnalium point crystalline substance of doping Stone), the combining forms such as four combination.In addition, rare earth element can be used and be doped in the metal oxide of doping, And rare earth element include it is one or more, rare earth element is, for example, lanthanum (La), cerium (Ce), yttrium (Y).
Moreover, it is noted that the segmentation in the material and the second electrode lay of the separating materials layer in first electrode layer The material of material layer can be identical or be also possible to difference.
The material selection of first electrode layer and the second electrode lay for composition electrode is as follows: according to the concrete function of electrode Difference, the two can have different selections.For example, first electrode layer is anode.So, anode can then be selected as metal electrode Or cermet electrodes.Further, the material of anode can be nickel or nickel alloy or nickeliferous ceramics.For example, the second electrode lay For cathode.So, cathode can then be selected as metal oxide electrode.Optionally, the material of metal oxide electrode is ternary Alloyed oxide or quaternary alloy oxide.Optionally, the metallic element in ternary alloy three-partalloy oxide includes the first element combinations Or second element combination, wherein the first element combinations include samarium, strontium, cobalt, therefore ternary alloy three-partalloy oxide can be SmxSryCoz (SSC).It can be with Sm in some specific examples0.5Sr0.5Co3O3.Second element combination includes lanthanum, strontium, cobalt, therefore.Ternary alloy three-partalloy Oxide can be LaxSryCoOz(LSC).In some specific examples, ternary alloy three-partalloy oxide can be La0.5Sr0.5CoO3。 Or cathode can be selected as perovskite electrode, such as LaSrCoO4、LaNiO3.Metallic element packet in quaternary alloy oxide Include lanthanum, strontium, cobalt, iron, such as LaxSryCoFeOz(LSCF).In some specific examples, quaternary alloy oxide can be La1- xSrxCo0.2Fe0.8O3(wherein 0.1 < x < 0.6).
As follows for the material selection for constituting the electrolyte layer of electrolyte: the material of electrolyte layer can be undoped gold Belong to the metal oxide of oxide or doping.Optionally, metal oxide includes zirconium oxide and cerium oxide.Optionally, doping Doped chemical in metal oxide is rare earth element, and rare earth element includes one or more.
Particularly, more narration in detail will be carried out to the network-like structure for being formed in electrode in example below.
It has been observed that network-like structure is designed for dividing electrode, in example, network-like structure is by separating materials Layer is constituted.Alternatively, network-like structure is made of separating materials layer and electrode material layer.When network-like structure is formed in first electrode When layer, network-like structure is made of separating materials layer or separating materials layer and first electrode material layer collectively form.When network-like When structure is formed in the second electrode lay, network-like structure is made of separating materials layer or separating materials layer and second electrode material layer It collectively forms.
It will (be only below that cathode is divided i.e. in film electrode structure with the second electrode lay for being provided with network-like structure; Certainly in other examples, also can choose is only anode be divided or anode and cathode be divided) for said It is bright.
In addition, usually can choose in the example of such cathode segmentation using anode as support.In other words, anode It plays and reinforces fuel cell, support electrolyte layer and cathode etc. are used.That is cathode segmentation, anode-supported.Similarly, fuel cell With anode segmentation, cathode support type;Alternatively, fuel cell has anode segmentation, cathode segmentation, electrolyte-supported type.
For cathode segmentation, anode-supported SOFC, divide cathode network-like structure can make under illustrate.
Film electrode structure 100 has structure as shown in Figure 1.According to orientation shown in FIG. 1, film electrode structure includes being located at The anode 102 of bottom is located in the middle electrolyte layer 103 and superposed cathode 104.Also, also have in cathode 104 In separating materials layer 105 arranged in a vertical direction, separating materials layer 105 has run through cathode 104.
Although anode, cathode and electrolyte layer have opposite thickness size, for example, anode 102 in Fig. 1 Thickness be greater than the thickness of cathode 104, the thickness of cathode 104 is greater than the thickness of electrolyte layer 103.But cathode of the present invention, sun The thickness of pole and electrolyte layer particularly limiting, can be needed according to specific manufacture craft and function and select into Row adjustment.However, it should be understood that in most film electrode structure, thickness of the thickness of electrolyte layers relative to cathode Thickness with anode is all smaller.
The thickness of separating materials layer 105 can also carry out adjustment appropriate.For example, the thickness of separating materials layer 105 is equal to The thickness of cathode 104;Alternatively, the thickness of separating materials layer 105 be less than cathode 104 thickness (this can in subsequent narration quilt It refers to, and can also be illustrated from Fig. 6).
Separating materials layer is intended for the example of network-like structure and divides electrode, therefore, the shape of separating materials layer Shape can have the scheme of plurality of optional, and is limited with that can play substantially segmentation electrode.Generally, separating materials layer is to connect Continuous body structure or discrete bodies structure.In the example for the thickness that the thickness of separating materials layer is equal to cathode, when separating materials layer is When Continuum Structure, cathode is discrete;Of course, when separating materials layer is discrete bodies structure, cathode is Continuum Structure 's.
In the example for the thickness that the thickness of separating materials layer is less than cathode, separating materials layer is Continuum Structure or discrete When structure, cathode is all that continuously, cathode is divided material layer (discrete) in the part of neighbouring electrolyte layer.And due to dividing material The thickness of the bed of material is less than the thickness of cathode, and therefore, cathode also has the part of covering separating materials layer, and the covering part is Continuously.In other words, in such an example, so-called cathode is the covering for continuously referring to aforementioned a part for belonging to cathode Part.
It optionally, include that the first regular figure or first are non-as the shape of the Continuum Structure of exemplary separating materials layer Regular figure.Wherein, the first regular figure includes array shape, honeycombed.The hole of array shape may be, for example, triangle, quadrangle or Polygon;
Optionally, separating materials layer is discrete bodies structure, and the shape of discrete bodies structure includes Second Rule figure or second Irregular figure, it is highly preferred that Second Rule figure is forked.Second Rule figure, such as can be and the first regular figure Identical shape, naturally it is also possible to be and the different figure of the first regular figure institute.
The cathode that arrangement above has separating materials layer is more clearly understood that and implemented for the ease of those skilled in the art, is asked Refering to Fig. 2-Fig. 5.
By taking Fig. 2 as an example, wherein greyish black color part is in cathode because of the region 1041a (electrode material that is divided to form Layer), white portion is separating materials layer 105a.On the whole, tessellate is presented in cathode 104.Wherein, cathode has compartment of terrain in length and breadth 12 × 12 region 1041a of arrangement.Each region is the electrode material layer that electrode material (LSC as the aforementioned) is formed, and electric Pole material layer is discrete bodies.Separating materials layer 105a have be spaced in length and breadth and alternately arrange 11 × 11 latitude and longitude/bands/ Item, and separating materials layer is non-individual body.
By taking Fig. 3 as an example, wherein greyish black color part is in cathode because of the region 1041b that is divided to form, substantially three The combination shape structure of regular hexagon, and be discrete bodies.White portion is separating materials layer 105b, the group of substantially multiple line segments It closes, and is non-individual body.
By taking Fig. 4 as an example, wherein greyish black color part is substantially to be positive four in cathode because of the region 1041c that is divided to form Side shape structure, and be discrete bodies.White portion be separating materials layer 105c, the combination of substantially multiple line segments, and for connect Continuous body.
By taking Fig. 5 as an example, wherein greyish black color part is substantially to be positive four in cathode because of the region 1041d that is divided to form Side shape structure, and be non-individual body.White portion is separating materials layer 105d, " ten " word that substantially two line segments are composed Shape structure, it is multiple to be somebody's turn to do " ten " character form structure compartment of terrain arrangement and be discrete bodies.
It should be pointed out that the above structure as described in Fig. 2 to Fig. 5 can be only the part of cathode, in complete device Or in device, the structure of cathode usually can be the simple repetition of Fig. 2 structure in any figure into Fig. 5.For example, for Fig. 1 Shown in scheme, complete cathode construction can be being arranged in juxtaposition for two cathode constructions as shown in figure 1.
In addition, figure 2 above, into structure shown in fig. 5, the network-like structure for dividing cathode is by separating materials layer Constitute, and in such example, separating materials layer be through cathode (i.e. separating materials layer extends from electrolyte layer to cathode To the whole of cathode thickness).Further, separating materials layer processing has except structural form enumerated above, can be with With other construction (such as pentagon, triangles, etc. appropriate.), it is limited so that cathode can be split.
In other some examples, other cathode constructions are also possible to have structure similar with above-mentioned cathode.And The main distinction is, the network-like structure for dividing cathode is made of separating materials layer and electrode material layer, therefore in this way Example in, separating materials layer does not run through cathode, and (in other words, electrode material layer is covered on separating materials layer, that is, divides Material layer extends to the part of cathode thickness from electrolyte layer to cathode;In other words, separating materials layer is from electrolyte layer to cathode The top surface of cathode is extended close to, is formed between one fixed width between the top surface of separating materials and the top surface of the cathode Gap).Film electrode structure (fuel cell 200) can be illustrated in attached drawing as shown in FIG. 6 in this way.
Just it has been observed that being also resided in for dividing one of different factor of network-like structure of cathode other than its shape: The length difference D1 of separating materials (in the difference of the extended distance of the thickness direction of film electrode structure).In order to more clearly to this It is illustrated, referring to Fig. 6.
Film electrode structure (fuel cell 200) definition has thickness direction (shown in this filled arrows of Fig. 6), separating materials layer 205 have direction (the i.e. anode 102 to cathode 204 by first electrode layer (anode 102) to the second electrode lay (cathode 204) Direction) thickness D1, the distance between separating materials layer 205 to the top surface of cathode 204 be D2.The sum of D1 and D2 are cathode In the length of thickness direction.The value of D1 and D2 can freely be carried out selection cooperation, and the present invention is not specifically limited it. In example, D1 is with a thickness of 1~50 micron.Or thickness D1 is 6~45 microns;Alternatively, thickness D1 is 16~30 microns;Alternatively, Thickness D1 is 20~26 microns.Also, D1 is greater than D2.
In addition, being to be run through with separating materials layer and do not described through cathode respectively in examples above.But it answers Work as understanding, in other other examples, separating materials layer also can have other distribution modes, for example, partial point It cuts material layer and has run through cathode, and the separating materials layer of another part has run through cathode.
The above-mentioned film electrode structure (the first film electrode structure) to anode-supported, cathode segmentation is described.And it is right The main distinction in the film electrode structure (the second film electrode structure) that cathode support, anode are divided, with the first film electrode structure One of be: divided is the difference of which electrode (or can be two electrodes while being divided), and the side divided Formula may refer to 2~Fig. 5 of earlier figures.Further, for the film electrode structure of electrolyte-supported, cathode segmentation, anode segmentation (third film electrode structure), is with one of the first film electrode structure and the main distinction of the second film electrode structure, anode and Cathode is divided.Also, the partitioning scheme of cathode and anode can be selected as identical partitioning scheme or To be different partitioning scheme.
In addition, example Anodic of the present invention is supported below in order to make those skilled in the art be more easily performed the present invention, The film electrode structure preparation method of cathode segmentation is illustrated.
Make anode.The anode can use the cermet anode of Ni or Ni alloy.
Electrolyte is made on a face of anode.Electrolyte can use rear-earth-doped cerium oxide or rear earth doping oxygen Change zirconium.
Oxide network is made away from the surface of anode in electrolyte.Production method can be using silk-screen printing, ceramics spray Ink printing etc..
The structure made above is sintered, the temperature of sintering is 1000~1500 DEG C.
Then, it is provided with the surface coated cathode material of oxide network in electrolyte, is then burnt at 900~1200 DEG C Knot.
Film electrode structure in the prior art, including anode, electrolyte and cathode.And preparation method and the above method The main distinction be: the oxide network more than not making.
It is found by examining, in existing technology, in subsequent assembling process after being sintered to cathode or after sintering, Film electrode structure is easy to happen cracking or removing, and yield rate only has 40-60% or so.And use the method institute in example of the present invention The film electrode structure that the anode-supported of preparation, cathode are divided is in production and application process, and the cracking situation of cathode is by preferably Inhibit, yield rate is promoted to 95% or more.
In order to make those skilled in the art be more easily performed the present invention, to the production method of the film electrode structure in example into Row explanation.
Since solid oxide fuel cell has plate, cast, corrugated plate type, flat-tube type or other shapes etc. Various types of constructions, and film electrode structure proposed in example of the present invention can be adapted for the battery class of the above various constructions Type.
One, by anode-supported, cathode divide flat plate cell for, structure be anode/electrolyte/oxide network/ Cathode, the production method is as follows:
1, anode is prepared
Using the cermet anode (tabular) of the methods of curtain coating, extrusion forming preparation alloy containing Ni or Ni, such as Ni- YSZ, Ni-GDC anode etc., the percent by volume of Ni is between 20-80%.
2, anode/electrolyte is prepared
Electrolytic thin-membrane is prepared in anode surface using the methods of curtain coating, spin coating, silk-screen printing, material is rear-earth-doped Cerium oxide or rear-earth-doped oxidation zirconium, 1-50 microns of thickness.
3, anode/electrolyte/oxide network is prepared
Oxide network is prepared in electrolyte membrane surface using the methods of silk-screen printing, ceramic ink jet printing.Material: dilute Cerium oxide or rear-earth-doped oxidation zirconium, aluminium oxide, Mg-Al spinelle, silicate of soil doping etc., height: 1-50 microns.
4, sintered plate is prepared
Plate by anode/electrolyte/oxide network co-sintering, sintering temperature: 1200-1500 DEG C of sintering temperature.
5, flat plate cell processed
Cathode is formed on the oxide network surface of the above sintered plate.Cathode can choose LSC cathode, LSCF cathode or SSC cathode.The method for preparing cathode includes 900-1200 DEG C of sintering after coating.
It can have the various size selected such as 5cm × 5cm thus to obtain flat plate cell, 10cm × 10cm, 20cm × 20cm, 20cm × 30cm, 30cm × 50cm etc..
Two, by anode-supported, cathode divide tubular cells for, structure be anode/electrolyte/oxide network/ Cathode, the production method is as follows:
1, anode is prepared
Using the cermet anode (cast shape) of the methods of extrusion forming preparation alloy containing Ni or Ni, such as Ni-YSZ, Ni- GDC anode etc., the percent by volume of Ni is between 20-80%.
2, anode/electrolyte is prepared
Using the methods of silk-screen printing, dip-coating, electrophoresis, magnetron sputtering, plasma-deposited tubulose anode appearance For wheat flour for electrolytic thin-membrane, material is rear-earth-doped cerium oxide or rear-earth-doped oxidation zirconium, 1-50 microns of thickness.
3, anode/electrolyte/oxide network is prepared
Oxide network is prepared in electrolyte membrane surface using the methods of silk-screen printing, ceramic ink jet printing.Material: dilute Cerium oxide or rear-earth-doped oxidation zirconium, aluminium oxide, Mg-Al spinelle, silicate of soil doping etc., height: 1-50 microns.
4, sintered pipes are prepared
By the anode/electrolyte of tubulose/oxide network co-sintering, sintering temperature: 1200-1500 DEG C of sintering temperature.
5, tubular cells processed
Cathode is formed on the oxide network surface of the above sintered pipes.Cathode can choose LSC cathode, LSCF cathode or SSC cathode.The method for preparing cathode includes 900-1200 DEG C of sintering after coating.
It should be understood that the various implementations of the film electrode structure in example of the present invention can be desirably used in The battery of various structural types (plate, cast, corrugated plate type, flat-tube type).Also, each structure and function in film electrode structure The material and its manufacture craft of ergosphere and the partitioning scheme of electrode can also be by on-demand selection collocation.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of film electrode structure, be applied to battery, which is characterized in that the film electrode structure with multi-layer structure include according to First electrode layer, the second electrode lay and the electrolyte layer of secondary lamination contact arrangement, the electrolyte layer are located at first electricity Between pole layer and the second electrode lay;
One of the first electrode layer and the second electrode lay and the two have network-like structure;
The network-like structure includes separating materials layer and optional electrode material layer, and the optional electrode material layer is located at institute It states between electrolyte layer and the electrode material layer;
The thermal expansion coefficient of the separating materials layer is less than or equal to the thermal expansion coefficient of the electrolyte layer.
2. film electrode structure according to claim 1, which is characterized in that the separating materials layer be Continuum Structure or from Granular media structure;
Preferably, the shape of the Continuum Structure includes the first regular figure or the first irregular figure, it is highly preferred that described First regular figure includes array shape, honeycombed, and the hole of the array shape is triangle, quadrangle or polygon;
Preferably, the separating materials layer be discrete bodies structure, the shape of the discrete bodies structure include Second Rule figure or Second irregular figure, it is highly preferred that the Second Rule figure is forked.
3. film electrode structure according to claim 1 or 2, which is characterized in that the separating materials layer has by the first electricity The thickness in pole layer to the direction of the second electrode lay, and it is described with a thickness of 1~50 micron, it is preferable that it is described with a thickness of 6~45 Micron, it is highly preferred that it is described with a thickness of 16~30 microns, it is further preferred that described with a thickness of 20~26 microns.
4. film electrode structure according to claim 1, which is characterized in that the material of the separating materials layer include doping or Undoped cerium oxide, doped or non-doped zirconium oxide, aluminium oxide, magnesium aluminate spinel, in silicate any one or it is more The combination of kind, it is preferable that the cerium oxide of doping and the zirconium oxide of doping are all made of rare earth element and are doped, and rare earth element packet It includes one or more.
5. film electrode structure according to claim 1 or 4, which is characterized in that the first electrode layer and second electricity Pole layer all has network-like structure, and in the material and the second electrode lay of the separating materials layer in the first electrode layer The material of separating materials layer is identical or different.
6. film electrode structure according to claim 1, which is characterized in that the first electrode layer is anode, and the sun Extremely metal electrode or cermet electrodes, it is preferable that the material of the anode is nickel or nickel alloy or nickeliferous ceramics.
7. film electrode structure according to claim 1, which is characterized in that the second electrode lay is cathode, and the yin Extremely metal oxide electrode, the material of the metal oxide electrode are ternary alloy three-partalloy oxide or quaternary alloy oxide, Preferably, the metallic element in the ternary alloy three-partalloy oxide includes that the first element combinations or second element combine, wherein described First element combinations include lanthanum, strontium, cobalt, and the second element combination includes samarium, strontium, cobalt, in the quaternary alloy oxide Metallic element includes lanthanum, strontium, cobalt, iron.
8. film electrode structure according to claim 1, which is characterized in that the material of the electrolyte layer include it is undoped or The metal oxide of doping, it is preferable that the metal oxide includes zirconium oxide and cerium oxide, it is highly preferred that the doping Doped chemical in metal oxide is rare earth element, and rare earth element includes one or more.
9. a kind of fuel cell, which is characterized in that including the film electrode structure as described in any one of claim 1~8.
10. a kind of battery pile, which is characterized in that including at least two fuel cells as claimed in claim 9, adjacent two It is connected between the fuel cell by bipolar plates.
CN201910280009.5A 2019-04-09 2019-04-09 A kind of film electrode structure, fuel cell and battery pile Pending CN109860676A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050181253A1 (en) * 2003-08-07 2005-08-18 Caine Finnerty Anode-supported solid oxide fuel cells using a cermet electrolyte
CN1667860A (en) * 2005-04-07 2005-09-14 天津大学 Fuel battery structure and process for preparing same
US20060234100A1 (en) * 2005-04-19 2006-10-19 Day Michael J Self-supporting ceramic membranes and electrochemical cells and cell stacks including the same
CN102148384A (en) * 2010-02-09 2011-08-10 三洋电机株式会社 Composite membrane, fuel cell and preparation method of composite membrane
CN209607852U (en) * 2019-04-09 2019-11-08 深圳市致远动力科技有限公司 A kind of film electrode structure, fuel cell and battery pile

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050181253A1 (en) * 2003-08-07 2005-08-18 Caine Finnerty Anode-supported solid oxide fuel cells using a cermet electrolyte
CN1667860A (en) * 2005-04-07 2005-09-14 天津大学 Fuel battery structure and process for preparing same
US20060234100A1 (en) * 2005-04-19 2006-10-19 Day Michael J Self-supporting ceramic membranes and electrochemical cells and cell stacks including the same
CN102148384A (en) * 2010-02-09 2011-08-10 三洋电机株式会社 Composite membrane, fuel cell and preparation method of composite membrane
CN209607852U (en) * 2019-04-09 2019-11-08 深圳市致远动力科技有限公司 A kind of film electrode structure, fuel cell and battery pile

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